Tutton's salt

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Tutton's salts are a family of salts with the formula M2M'(SO4)2(H2O)6 (sulfates) or M2M'(SeO4)2(H2O)6 (selenates). These materials are double salts, which means that they contain two different cations, M+ and M'2+ crystallized in the same regular ionic lattice. [1] The univalent cation can be potassium, rubidium, caesium, ammonium (NH4), deuterated ammonium (ND4) or thallium. Sodium or lithium ions are too small. The divalent cation can be magnesium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc or cadmium. In addition to sulfate and selenate, the divalent anion can be chromate (CrO42−), tetrafluoroberyllate (BeF42−), hydrogenphosphate (HPO42−) [2] or monofluorophosphate (PO3F2−). Tutton's salts crystallize in the monoclinic space group P21/a. [3] The robustness is the result of the complementary hydrogen-bonding between the tetrahedral anions and cations as well their interactions with the metal aquo complex [M(H2O)6]2+.

Contents

Perhaps the best-known is Mohr's salt, ferrous ammonium sulfate (NH4)2Fe(SO4)2.(H2O)6). [4] Other examples include the vanadous Tutton salt (NH4)2V(SO4)2(H2O)6 and the chromous Tutton salt (NH4)2Cr(SO4)2(H2O)6. [5] In solids and solutions, the M'2+ ion exists as a metal aquo complex [M'(H2O)6]2+.

Related to the Tutton's salts are the alums, which are also double salts but with the formula MM'(SO4)2(H2O)12. The Tutton's salts were once termed "false alums". [6]

History

Tutton salts are sometimes called Schönites after the naturally occurring mineral called Schönite (K2Mg(SO4)2(H2O)6). They are named for Alfred Edwin Howard Tutton, who identified and characterised a large range of these salts around 1900. [7]
Such salts were of historical importance because they were obtainable in high purity and served as reliable reagents and spectroscopic standards.

Table of salts

M1M2formulanamea Åb Åc Åβ°V Å3colourNαNβNγBiaxial2Vother
KCdK2[Cd(H2O)6](SO4)2Potassium cadmium sulfate hexahydrate [8]
CsCdCs2[Cd(H2O)6](SO4)2caesium cadmium sulphate hexahydrate [9]
NH4Cd(NH4)2[Cd(H2O)6](SO4)2Ammonium Cadmium Sulfate Hydrate9.39512.7766.299106°43'727.63colourlessl.4861.4881.494Biaxial(-f)large [10] density=2.05 [11]

Slowly loses water in dry air. [12]

KCoK2[Co(H2O)6](SO4)2 [13] Potassium cobaltous sulfate [14] 6.1519.06112.207104.8°657.78 [15] reddensity=2.21
RbCoRb2[Co(H2O)6](SO4)2Rubidium hexaaquacobalt(II) sulphate6.249.1912.453105.99°686.5 [12] ruby-red [16] desnsity=2.56
CsCoCs2[Co(H2O)6](SO4)2Caesium hexaaquacobalt(II) sulphate9.318(1)12.826(3)6.3650(9)107.13(1)°727.0 [17] dark red
NH4Co(NH4)2[Co(H2O)6](SO4)2 [18] Cobaltous ammonium sulfate hexahydrate6.2429.25512.549106.98°693.3 [19] purple [20] density=1.89
TlCoTl2[Co(H2O)6](SO4)2Cobaltous thallium sulfate hexahydrate, Thallium hexaaquacobalt(II) sulfate,9.227(1)12.437(2)6.220(1)106.40(1)°684.7light red [21]
TlCoTl2[Co(H2O)6](SO4)2dithallium cobalt sulfate hexahydrate9.235(1)12.442(2)6.227(1)106.40(1)°yellowish pink1.5991.6131.624biaxial(-)medium large [22] density=4.180 g/cm3
RbCrRb2[Cr(H2O)6](SO4)2 [23] dirubidium chromium sulfate hexahydrate
CsCrCs2[Cr(H2O)6](SO4)2 [23] dicaesium chromium sulfate hexahydrate
ND4Cr(ND4)2Cr(SO4)2 · 6 H2O [23] dideuterated ammonium chromium sulfate hexahydratebright blue,formed from with ammonium sulfate in minimal water under nitrogen gas. Stable in air from oxidation, but may dehydrate. [24]
KCuK2[Cu(H2O)6](SO4)2 cyanochroite [14] 9.2712.446.30104.47 [25] 663.0 [25] pale green bluedensity=2.21 [25] within unit cell 7.76 between two Cu atoms [26]
RbCuRb2[Cu(H2O)6](SO4)2Dirubidium hexaaquacopper sulfate9.26712.3666.228105°19'686.8brilliant greenish blue1.4881.4911.506biaxial (+) [27] mediumdensity=2.580g/cm3 [10] Cu-O 2.098 Å Rb-O 3.055 Å. [27]
CsCuCs2[Cu(H2O)6](SO4)2 [28] dicaesium hexaaquacopper sulfate9.43912.7626.310106°11'718.5brilliant greenish blue,1.5041.5061.514biaxial (+)density=2.864g/cm3 [29]
NH4Cu(NH4)2[Cu(H2O)6](SO4)2ammonium hexaaquacopper(II) sulfate [30] 6.3112.389.22106.16°691.25 [31] density=1.921; [31] heat of formation=-777.9 kcal/mol [31] Jahn-Teller distortion axis switches under pressure of ~1500 bars, a,b axis shrinks 3.3% and 3.5% and c axis extends 4.5%. [30]
TlCuTl2[Cu(H2O)6](SO4)2Thallium copper sulfate hydrate9.26812.3646.216105°33'brilliant greenish blue1.6001.6101.620biaxialvery large [32] density=3.740 g/cm3
KFeK2[Fe(H2O)6](SO4)2dipotassium iron sulfate hexahydrate [14]
RbFeRb2[Fe(H2O)6](SO4)2Rubidium iron sulfate hydrate9.21812.4976.256105°45'pale green1.4801.4891.501biaxial (+)large,density=2.523g/cm3 [33]
CsFeCs2[Fe(H2O)6](SO4)2Caesium hexaaquairon(II) sulphate9.357(2)12.886(2)6.381(1)106.94(1)°736.0dark yellow [17] very pale green1.5011.5041.516biaxial (+)medium [34] density=2.805
NH4Fe(NH4)2[Fe(H2O)6](SO4)2 mohrite [14] 6.24(1)12.65(2)9.32(2)106.8(1)704.28vitreous pale greendensity=1.85 named after Karl Friedrich Mohr [35]
TlFeTl2[Fe(H2O)6](SO4)2Thallium hexaaquairon(II) sulfate9.262(2)12.497(1)6.235(2)106.15(1)°693.2 [21] light green1.5901.605=1.616biaxial (-)largedensity=3.662g/cm3 [36]
KMgK2[Mg(H2O)6](SO4)2 picromerite 9.0412.246.095104° 48' [14] colourless or white1.4601.4621.472biaxial (+)mediumdensity=2.025g/cm3; [37] expanded second coordination sphere around Mg. [14]
RbMgRb2[Mg(H2O)6](SO4)2rubidium magnesium sulphate hexahydrate [38] 9.23512.4866.224105°59'colourless1.4671.4691.476 [39] biaxial
CsMgCs2[Mg(H2O)6](SO4)2Caesium hexaaquamagnesium sulphate9.338(2)12.849(4)6.361(2)107.07(2)°729.6colourless [17] 1.4811.4851.492biaxial(+)mediumdensity=2.689 [40]
NH4Mg(NH4)2[Mg(H2O)6](SO4)2 boussingaultite 9.2812.576.2107°6' [14] [18]
NH4Mg(NH4)2[Mg(H2O)6](SO4)2Ammonium Magnesium Chromium Oxide Hydrate9.508±.00112.6746.246106°14'bright yellow1.6371.6381.653biaxial(+)smalldensity=1.840 g/cm 3 [10]
TlMgTl2[Mg(H2O)6](SO4)2 [41] dithallium magnesium sulfate hexahydrate9.22 9.262(2)12.42 12.459(2)6.185 6.207(1)106°30' 106.39(2)°687.1colourless [21] density=3.532 g/cm3
RbMnRb2[Mn(H2O)6](SO4)2Dirubidium hexaaquamanganese sulfate(VI)9.282(2)12.600(2)6.254(2)105.94(2)703.3Å3 [42] [43]
CsMnCs2[Mn(H2O)6](SO4)2Caesium hexaaquamanganese(II) sulphate9.418(3)12.963(2)6.386(3)107.17(4)°744.9pale pink [17] purplish white [44] 1.4951.4971.502biaxial(+)largedensity=2.763 [44]
NH4Mn(NH4)2[Mn(H2O)6](SO4)2manganese ammonium sulfate hexahydrate9.4012.746.26107.0° [45] pale pink1.4821.4561.492biaxial(+)largedensity=1.827 [46]
TlMnTl2[Mn(H2O)6](SO4)2Thallium manganese sulfate hexahydrate9.3276(6), 9.322(2)12.5735(8), 12.565(2)6.2407(4), and 6.233(1)106.310(3)° [47] 106.29(2)°,700.8 [21] light pink
KNiK2Ni(SO4)2 · 6 H2O [13] Potassium Nickel Sulfate Hexahydrate [14] used as UV filter [48]
RbNiRb2[Ni(H2O)6](SO4)2Rubidium Nickel Sulfate Hexahydrate6.22112.419.131106.055°677.43001 surface has step growth of 4.6 Å, optical transmission bands at 250, 500 and 860 nm which are the same as nickel sulfate hexahydrate, but UV band transmits more. Heavy absorption 630-720 nm and 360-420 nm3 density 2.596 g cm−3. [48] stable to 100.5 °C solubility in g/100ml=0.178t + 4.735 MW=529.87
CsNiCs2[Ni(H2O)6](SO4)2Caesium hexaaquanickel(II) sulphate, Caesium Nickel Sulfate Hexahydrate9.259(2)12.767(2)6.358(1)107.00(2)°718.7 [17] greenish blue1.5071.5121.516biaxial(-)very largedensity=2.883 [49] used as UV filter [48]
NH4Ni(NH4)2[Ni(H2O)6](SO4)2 nickel-boussingaultite [14] [50] 9.18612.4686.424684.0blueish green. [51] [52] density=1.918 cas=51287-85-5
TlNiTl2[Ni(H2O)6](SO4)2Thallium hexaaquanickel(II) sulfate9.161(2)12.389(2)6.210(2)106.35(2)°676.3greenish blue [21] 1.6021.6151.620biaxial(-)largedensity=3.763 [53]
KRuK2[Ru(H2O)6](SO4)2 [54] 8.95012.2686.135105.27644
RbRuRb2[Ru(H2O)6](SO4)2 [54] 9.13212.5276.351106.30
KVK2[V(H2O)6](SO4)2Vanadium(II) potassium sulfate hexahydrate [55]
RbVRb2[V(H2O)6](SO4)2Rubidium vanadium(II) sulfate
NH4V(NH4)2[V(H2O)6](SO4)2Vanadium(II) ammonium sulfate hexahydrate9.4212.766.22107.2°714.2amethystdensity=1.8 V-O length 2.15Å [56]
KZnK2[Zn(H2O)6](SO4)2 [13] [14] dipotassium zinc sulphate hexahydrate9.04112.3106.182104.777°colourless1.4781.4811.496biaxiallargedensity=2.242g/cm3 [57] Thermal decomposition at 252K. [58]
RbZnRb2[Zn(H2O)6](SO4)2Rubidium Zinc Sulphate Hexahydrate [59] 9.18512.4506.242105°54'colourless1.4831.4891.497biaxiallarge [60]
CsZnCs2[Zn(H2O)6](SO4)2zinc caesium sulphate hexahydrate [61] 9.314(2)12.817(2)6.369(2)106.94(2)°727.3colourless [17] 1.5071.6101.615biaxial(-)largedensity=2.881 [62]
NH4Zn(NH4)2[Zn(H2O)6](SO4)29.20512.4756.225106°52' [18] 684.1heat of fusion 285 J/g [63]
TlZnTl2[Zn(H2O)6](SO4)2Thallium hexaaquazinc(II) sulfate [64] 9.219(2)12.426(2)6.226(1)106.29(2)°684.6colourless [21]
selenates
CsNiCs2[Zn(H2O)6](SeO4)2Dicaesium nickel selenate hexahydrate [65] 7.46747.915211.7972106.363669.04light green
RbCuRb2[Cu(H2O)6](SeO4)2Dirubidium copper selenate hexahydrate [66] 6.36312.4319.373104.33718.3

Organic salts

Some organic bases can also form salts that crystallise like Tutton's salts.

formulanamea Åb Åc Åβ°V Å3colourNαNβNγBiaxial2Vother
(C4H12N2)[Zn(H2O)6](SO4)2piperazinediium hexaaquazinc(II) bis(sulfate) [67] 12.956210.650213.3251114.0321679.30Colourless
cadmium creatininium sulfate [68] 6.558427.8717.1955110.3711232.99colourless

Related Research Articles

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<span class="mw-page-title-main">Magnesium sulfate</span> Chemical compound with formula MgSO4

Magnesium sulfate or magnesium sulphate is a chemical compound, a salt with the formula MgSO4, consisting of magnesium cations Mg2+ (20.19% by mass) and sulfate anions SO2−4. It is a white crystalline solid, soluble in water but not in ethanol.

<span class="mw-page-title-main">Copper(II) sulfate</span> Chemical compound

Copper(II) sulfate, also known as copper sulphate, is an inorganic compound with the chemical formula CuSO4. It forms hydrates CuSO4·nH2O, where n can range from 1 to 7. The pentahydrate (n = 5), a bright blue crystal, is the most commonly encountered hydrate of copper(II) sulfate, while its anhydrous form is white. Older names for the pentahydrate include blue vitriol, bluestone, vitriol of copper, and Roman vitriol. It exothermically dissolves in water to give the aquo complex [Cu(H2O)6]2+, which has octahedral molecular geometry. The structure of the solid pentahydrate reveals a polymeric structure wherein copper is again octahedral but bound to four water ligands. The Cu(II)(H2O)4 centers are interconnected by sulfate anions to form chains.

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Double salt</span> Type of salt

A double salt is a salt that contains two or more different cations or anions. Examples of double salts include alums (with the general formula MIMIII(SO4)2·12H2O) and Tutton's salts (with the general formula (MI)2MII(SO4)2·6H2O). Other examples include potassium sodium tartrate, ammonium iron(II) sulfate (Mohr's salt), potassium uranyl sulfate (used to discover radioactivity) and bromlite BaCa(CO3)2. The fluorocarbonates contain fluoride and carbonate anions. Many coordination complexes form double salts.

<span class="mw-page-title-main">Silver sulfate</span> Chemical compound

Silver sulfate is the inorganic compound with the formula Ag2SO4. It is a white solid with low solubility in water.

Indium(III) sulfate (In2(SO4)3) is a sulfate salt of the metal indium. It is a sesquisulfate, meaning that the sulfate group occurs 11/2 times as much as the metal. It may be formed by the reaction of indium, its oxide, or its carbonate with sulfuric acid. An excess of strong acid is required, otherwise insoluble basic salts are formed. As a solid indium sulfate can be anhydrous, or take the form of a pentahydrate with five water molecules or a nonahydrate with nine molecules of water. Indium sulfate is used in the production of indium or indium containing substances. Indium sulfate also can be found in basic salts, acidic salts or double salts including indium alum.

<span class="mw-page-title-main">Nickel(II) sulfate</span> Chemical compound

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<span class="mw-page-title-main">Ammonium iron(II) sulfate</span> Chemical compound

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<span class="mw-page-title-main">Cobalt(II) sulfate</span> Inorganic compound

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<span class="mw-page-title-main">Vanadium(II) sulfate</span> Chemical compound

Vanadium(II) sulfate describes a family of inorganic compounds with the formula VSO4(H2O)x where 0 ≤ x ≤ 7. The hexahydrate is most commonly encountered. It is a violet solid that dissolves in water to give air-sensitive solutions of the aquo complex. The salt is isomorphous with [Mg(H2O)6]SO4. Compared to the V–O bond length of 191 pm in [V(H2O)6]3+, the V–O distance is 212 pm in the [V(H2O)6]SO4. This nearly 10% elongation reflects the effect of the lower charge, hence weakened electrostatic attraction.

Nickel is one of the metals that can form Tutton's salts. The singly charged ion can be any of the full range of potassium, rubidium, cesium, ammonium (), or thallium. As a mineral the ammonium nickel salt, (NH4)2Ni(SO4)2 · 6 H2O, can be called nickelboussingaultite. With sodium, the double sulfate is nickelblödite Na2Ni(SO4)2 · 4 H2O from the blödite family. Nickel can be substituted by other divalent metals of similar sized to make mixtures that crystallise in the same form.

<span class="mw-page-title-main">Nickel oxyacid salts</span>

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<span class="mw-page-title-main">Sulfate carbonate</span> Class of chemical compounds

The sulfate carbonates are a compound carbonates, or mixed anion compounds that contain sulfate and carbonate ions. Sulfate carbonate minerals are in the 7.DG and 5.BF Nickel-Strunz groupings.

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Gallium(III) sulfate refers to the chemical compound, a salt, with the formula Ga2(SO4)3, or its hydrates Ga2(SO4)3·xH2O. Gallium metal dissolves in sulfuric acid to form solutions containing [Ga(OH2)6]3+ and SO42− ions. The octadecahydrate Ga2(SO4)3·18H2O crystallises from these solutions at room temperature. This hydrate loses water in stages when heated, forming the anhydrate Ga2(SO4)3 above 150 °C and completely above 310 °C. Anhydrous Ga2(SO4)3 is isostructural with iron(III) sulfate, crystallizing in the rhombohedral space group R3.

References

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  27. 1 2 Ballirano, Paolo; Girolamo Belardi (2007). "Rietveld refinement of the Tutton's salt from parallel-beam X-ray powder diffraction data". Acta Crystallographica Section E. 63 (2): i56–i58. doi:10.1107/S1600536807002656. ISSN   1600-5368.
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  30. 1 2 Simmons, Charles J.; Michael A. Hitchman; Horst Stratemeier; Arthur J. Schultz (1993). "High-pressure, low-temperature, single-crystal neutron diffraction study of deuterated and hydrogenous ammonium hexaaquacopper(II) sulfate (Tutton's salt): a pressure-switchable Jahn-Teller distortion". Journal of the American Chemical Society. 115 (24): 11304–11311. doi:10.1021/ja00077a032. ISSN   0002-7863.
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  33. ↑ Swanson, H. E.; H. F. McMurdie; M. C. Morris; E. H. Evans (September 1970). "Standard X-ray Diffraction Powder Patterns" (PDF). National Bureau of Standards Monograph 25 Section 8. National Bureau of Standards. p. 64. Retrieved 16 June 2013.
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  38. ↑ Somasekharam, V.; Y.P. Reddy (1985). "Spectroscopic studies on vanadyl ion in rubidium magnesium sulphate hexahydrate". Solid State Communications. 53 (8): 695–697. Bibcode:1985SSCom..53..695S. doi:10.1016/0038-1098(85)90380-1. ISSN   0038-1098.
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  41. ↑ Chand, Prem; R. Murali Krishna; J. Lakshmana Rao; S. V. J. Lakshman (1993). "EPR and optical studies of vanadyl complexes in two host-crystals of Tutton salts of thallium". Radiation Effects and Defects in Solids. 127 (2): 245–254. Bibcode:1993REDS..127..245C. doi:10.1080/10420159308220322. ISSN   1042-0150.
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  54. 1 2 Bernhard, Paul; Ludi, Andreas (March 1984). "Infrared and Raman spectra of the hexaaquaruthenium ions: normal-coordinate analysis for and ". Inorganic Chemistry. 23 (7): 870–872. doi:10.1021/ic00175a015.
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  58. ↑ Lim, Ae Ran; Kim, Sun Ha (23 July 2015). "Structural and thermodynamic properties of Tutton salt K2Zn(SO4)2·6H2O". Journal of Thermal Analysis and Calorimetry. 123 (1): 371–376. doi:10.1007/s10973-015-4865-9. S2CID   93389171.
  59. ↑ Somasekharam, V; Prasad, P Siva; Ramesh, K; Reddy, Y P (1 February 1986). "Electronic Spectra of VO and Cu Ions in Rubidium Zinc Sulphate Hexahydrate". Physica Scripta. 33 (2): 169–172. Bibcode:1986PhyS...33..169S. doi:10.1088/0031-8949/33/2/014. S2CID   250762626.
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  63. ↑ Voigt, W.; S. Göring (1994). "Melting of Tutton's salts studied by DSC". Thermochimica Acta. 237 (1): 13–26. doi:10.1016/0040-6031(94)85179-4. ISSN   0040-6031.
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  65. ↑ Yankova, Rumyana; Genieva, Svetlana (June 2019). "Crystal structure and IR investigation of double salt Cs2Ni(SeO4)2·4H2O". Chemical Data Collections. 21: 100234. doi:10.1016/j.cdc.2019.100234. S2CID   181399910.
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